Magnetic materials



Aug. 27, 1968 a. R. PULLIAM 3,399,072

MAGNET I C MATERIALS 4 Sheets-Sheet 1 Original Filed March 4, 1963 FIG. I

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INVENTOR. GEORGE R. PULLIAM AGENT Aug. 27, 1968 G. R. PULLIAM MAGNETIC MATERIALS Original Filed March 4, 1963 4 Sheets-Sheet 5 FIG. 7

Llnllii 4 mar 5/5 5 7 7.7 b/ 5/ 5 7 V V s s s- INVENTOR.

GEORGE R. PULLIAM FIG. 8

AGENT Aug. 27, 1968 G. R. PULLIAM MAGNETIC MATERIALS 4 Sheets-Sheet 4 Original Filed March 4, 1963 INVENTOR. GEORGE R. PULL'AM AGENT United States Patent 3,399,072 MAGNETIC MATERIALS George R. Pulliam, La Mirada, Califi, assignor to North American Rockwell Corporation, a corporation of Delaware Continuation of application Ser. No. 262,742, Mar. 4, 1963. This application Apr. 14, 1967, Ser. No. 631,104

Claims. (Cl. 117-62) ABSTRACT OF THE DISCLOSURE A process for e'pitaxially growing a spinel ferrite on a substrate of MgO. The process comprises the steps of vaporizing, in a chamber, one or more compounds of the class consisting of FeBr MgBr MnBr CoBr NiBr ZnBr and CuBr and introducing water vapor and sufl'icient oxygen into the chamber, thereby to cause a spinel ferrite, derived 'at least in part from the vaporized compounds, to be deposited in epitaxial relation with the MgO substrate. The reaction takes place at a temperature above 500 C.

The present invention is a continuation of application Ser. No. 262,742, entitled, Magnetic Materials, now abandoned.

This invention relates to a method of producing magnetic crystalline structure.

Magnetic materials are finding increasingly wider usage in the field of electronics, where they form the basis of various components such as transformers, inductances, magnetic tapes, memory devices for computers, and the like. Since these difierent components generally require different magnetic characteristics, a great deal of research has been undertaken to provide magnetic materials having suitable magnetic characteristics. One result of this research is the development of a class of magnetic materials known as ferrites; the various members of this class having various magnetic characteristics and crystalline arrangements.

In the field of magnetic memory devices for computers, it is a basic requirement that the magnetic material should be magnetizable in one given direction, or in the opposite direction, in order to represent discrete on and oli states; any other direction, or state, being undesirable. Moreover, a minimal-strength energizing-magnetic field should cause the magnetic material to switch from one state to the other.

It has been found that both the magnetic material and its physical configuration are factors in the operation of the memory device.

In the past, two principal approaches have been used to form the magnetic material into the optimum physical configuration. One approach used extremely small groups of crystals, either deposited on a suitable substrate, or held together by a suitable binder; thus forming a polycrystalline arrangement. Of course, in this poly-crystalline arrangement the axes of the individual crystals are oriented in random directions.

A second, mono-crystalline approach, was to grow a large crystalwhich may be visualized, for convenience, as a plurality of individual crystals merged together in such a way that their axes are alined; thus forming a singe large crystal. This large crystal was then sliced, ground, cut, or shaped into the desired shape and size.

It is known that in magnetic materials there are certain magnetic directions relative to the axis of the crystal, in which the material may be magnetized easily; and that there are other directions relative to the axis of the crystal in which it is more difficult to magnetize the material.

In the poly-crystalline arrangement produced by the 3,399,072 Patented Aug. 27, 1968 ice first approach, the axes of he individual crystals were randomly oriented; and this random orientation of the axes of the individual crystals placed the magnetic directions of the individual crystals in random orientations. This condition does not provide optimum magnetic operation because an energizing magnetizing field finds some of the axes at the easy-to-magnetize direction, finds others are at the hard-to-magnetize direction, and finds still others at intermediate directions. This means that various portions of the magnetic material respond in different ways to an energizing field.

The mono-crystalline configuration of the second approach does not have the above disadvantage; because there the axes of all the individual crystals are alined in the same direction as a result of the crystal-growing proces. Thus, all portions of the single large crystals respond identically to an energizing magnetizing field.

Moreover, when using the mono-crystalline configuration, the subsequent shaping process may be controlled to take advantage of the easy-to-magnetize direction. For example, the large crystal may be cut, sliced, or ground in such a way that the easy-to-magnetize direction has a desired orientation relative to the energizing magnetizing field.

It is another characteristic of magnetic materials that in an extremely thin stratum, the direction of the magnetic moment (which is a function of electron spin, and need not be further discussed here) tends to remain in the plane of the stratum and does not point outward; that is, the film tends to become magnetically polarized in the plane of the strutum and not in the thin direction of the stratum.

For this reason, manufacturers try to produce a thinfilm poly-crystalline arrangement, one example being the well-known magnetic tape; although as indicated above, the poly-crystalline arrangement has the inherent disadvantage that the individual crystals are randomly oriented.

On the other hand, while the mono-crystalline arrangement has the inherent advantage of a single" axis, difliculty is experienced in producing an extremely thin slice.

Ideally, if a large single crystal can be grown and sliced so that the resultant thin stratum has its easy-to-magnetize direction in the plane of the stratum; and moreover if this stratum is of a desired size and/ or shape, this thin-stratum arrangement approaches the ideal magnetic structure for a memory device.

It is therefore the principal object of my invention to provide a method for producing magnetic material.

The attainment of this object and others will be realized from the following specification, taken in conjunction with the drawings, of which FIG. 1 shows the directions of magnetization in a thin slab of magnetic material;

FIG. 2 shows, symbolically, the crystalline structure of magnesium oxide;

FIG. 3 shows, symbolically, the crystalline structure of a magnetic ferrite having a spinel crystalline arrangement;

FIG. 4 shows, symbolically, the crystalline structure of a magnetic spinel ferrite combined with a magnesiumoxide substrate;

FIG. 5 shows exemplary apparatus;

FIG. 6 shows deposition conditions;

FIG. 7 shows a magnetic hysteresis loop;

FIG. 8 shows a composite magnetic memory device prepared in accordance with my invention; and

FIG. 9 shows an alternate orientation of current conductors in the memory device of FIG. 8.

Broadly stated, :my invention comprises the method of producing a thin film of magnetic material in the form of a single-crystal. This is achieved by forming a single crystal of magnetic material on a substrate, the substrate and 3 the magnetic material having crystalline arrangements that are conducive to an epitaxial relation that produces the above result.

The desired, ideal, thin-film magnetic structure can be achieved by following the teachings of my inventive conce t.

1 1G. 1 depicts a thin slab of magnetic material. Since in a thin slab the magnetic moments are in the plane of the slab, as previously indicated, the magnetic moments of slab 10 can be oriented in a longitudinal manner as shown by arrows 12 and 14; or in a transverse manner as shown by arrows 16 and 18; and in each manner the magnetic moment may point in either of the two opposite directions to represent on and off states.

If, for example, the longitudinal direction were the easy-to-magnetize direction, this would mean that the magnetic moments would easily assume the directions shown by the longitudinal arrows 12 and 14; i.e., a minimalstrength energizing magnetizing field could orient the mag netic moments in the direction of arrow 12 or 14. Reversing the energizing magnetic field would re-orient the magnetic moments to assume the opposite direction.

On the other hand, the magnetic moments would assume the directions shown by transverse arrows 16 and 18 only with a greater difiiculty; i.e., this would require a much stronger energizing magnetic field. In other words, a minimal-strength energizing magnetic field would not orient the magnetic moments in the transverse directions 16, 18.

Hence, in thin slab 10, a minimal-strength energizing magnetic field, requiring a minimal amount of external power, would assure that the magnetic material would have only two oppositely-directed magnetic states.

It will therefore be realized if the thin slab of magnetic material as shown in FIG. I were a single crystal, it would have a number of extremely desirable characteristics. Firstly, it would be easily magnetized either in direction 12 or direction 14; secondly; this magnetization would be achieved with a minimum amount of energy; thirdly, all portions of the slab would respond in an identical manner; fourthly, the material would not become magnetized in the transverse direction; and finally, since there would be only two directions of magnetization, the direction of magnetization at any given instant would be easily detected by a relatively simple sensing device.

One of the most useful magnetic materials is the compound Fe O which is a member of the class designated as ferrites. Moreover, it has a spinel type crystalline structure, and is therefore known as a spinel ferrite; the term spinel designating a type of crystalline structure first found in the mineral known as spinel.

Through the use of the process of my invention, it is possible to produce a single large crystal of magnetic spinel ferrite, Fe O in the form of a thin film, on a substrate of magnesium oxide, MgO.

Magnesium oxide makes an extremely good substrate, since it is non-magnetic; and therefore does not add to, or detract from the operation of the magnetic material. Moreover, a crystal of magnesium oxide has a desirable crystalline structure, which may be understood from FIG. 2.

FIG. 2 depicts a crystal 20 of magnesium oxide, MgO; the large circles 22 representing the positions of the oxygen ions, while the small circles 24 represent the positions of the magnesium ions.

FIG. 3 depicts a crystal 26 of a spinel, Fe O in this case; the large circles 22 again representing the positions of the oxygen ions; the smallest circles 28 representing the positions of iron ions; and the medium-sized circles '30 representing the positions of metallic ions, whose influance will be discussed later.

The similarity between the positions of the oxygen ions (large circles 20) in FIGS. 2 and 3 will be readily apparent.

My basic inventive concept is to deposit a crystal of a spinel ferrite, such as Fe O exemplified by crystal 26 of FIG. 3, onto a magnesium oxide crystal 20 as shown in FIG. 2; the combination then appearing as shown in FIG, 4.

The similarity in configuration and size of the spinel ferrite crystal 26 and the magnesium oxide crystal 20 is such that the oxygen ions are located at identical positions in both crystals. Thus, when an individual crystal 26 of the ferrite spinel is deposited onto an individual crystal 20 of magnesium oxide, the oxygen ions of the deposited ferrite spinel appear as a continuation of the magnesium oxide structure. Only the positions of the metallic ions of the spinel are different from the positions of the magnesium ions of the substrate. Therefore, the upper, deposited, ferrite spinel crystal 26 is oriented in such a manner that its axes have a given orientation relative to the axes of the lower magnesium oxide crystal 20.

If a magnesium oxide crystal of twice the size were used as a substrate, then two crystals of the spinel ferrite could be deposited onto this substrate; and the two deposited crystals would merge to form a larger, single crystal whose axes would be oriented in the same direction as the axes of the original single crystal previously described.

Similarly, if the magnesium oxide substrate were three or four times the size of the previously described example, the deposited spinel ferrite would form a triple or quadruple-sized crystal whose axes would be in the same direction as in the previous cases.

This regular repetitious orientation of axes in a given direction relative to a substrate is known as an epitaxial relation; and in the above case is due to the similarity between the size and crystalline structures of the substrate and the deposited material.

If, now, a large magnesium oxide crystal were ground and etched to form a smooth-surfaced substrate, a large single spinel ferrite crystal could be formed thereon, with the axes of the magnetic material in a given orientation, as determined by the substrate. Thus, the resultant ferrite would be a single crystal as large as the basic magnesium oxide crystal, and could be as thick or as thin as desired. In this way an epitaxial film of magnetic ferric oxide of desired thickness may be produced on a magnesium oxide substrate.

In accordance with my invention, the magnesium oxide substrate comprises a large crystal, which is readily available commercially. Onto this substrate I deposit, by means to be specifically described later, a ferrite crystal. In this way, the deposited ferrite crystal is epitaxial to the substrate; the ferrite crystal can be as thick or as thin as desired; and can be as large as the magnesium oxide substrate.

By making the deposited ferrite only a few microns thick, it is formed into a thin film of magnetic material that has the desirable magnetic characteristics discussed above.

The invention thus comprises the method of producing on a substrate, specifically MgO, a crystal of magnetic material positioned on said substrate in an epitaxial relation therewith.

THE INVENTIVE PROCESS The processes defined by the following chemical equations are such that stoichiometric quantities of the given compounds react in accordance with the prevailing temperatures, pressures, vapor pressures, concentrations, and other factors.

A two-step chemical reaction may be used. In step one, ferrous oxide (FeO) is deposited onto a magnesium oxide substrate, as exemplified by Equation I1 shown below.

FeBr +H O FeO-t-ZHBrt (I I This may be done by heating ferric bromide in a chamber to form a ferric bromide atmosphere; suspending the magnesium-oxide crystal in this atmosphere; and introducing moisture. The moisture (H O) is mostly conveniently introduced by a stream of humid air, or by a moist insert gas such as helium. The use of an inert gas minimizes the possibility of reversing the process of Equation I1.

I have found that maintaining the bromide vapor and the magnesium oxide crystal at a temperature in the range of 500 C. to 800 C. is satisfactory; although at 700 C. the vapor pressure of ferric bromide provides a desirable ratio of ferric bromide to air or helium.

If desired, hydrogen and oxygen may be used instead of the air and moisture, since in the process of Equation I1 the moisture breaks down into hydrogen and oxygen.

In the second step of the two-step chemical reaction, the ferrous oxide (FeO) is oxidized to form ferrousferric oxide (Fe O by the introduction of oxygen or carbon dioxide into the chamber; these chemical reactions being exemplified by Equations 12.1 and 12.2.

Thus, the desired Fe O is produced on the MgO substrate.

Rather than using the above-described two-step chemical reaction, a one-step chemical reaction may alternatively be used; and Fe O may be formed directly by use of a reaction exemplified in Equation Ill.

Regardless of whether the one-step or the two-step chemical reaction is used, the fi al result is a thin la er of magnetic material, Fe O on a substrate of non-magnetic material, magnesium oxide; the magnetic material being an epitaxial thin film of desired thickness.

It was previously indicated that Fe O has a spinel crystalline structure. The general formula for a spinel ferrite may be written as (A,B)+ (C,D) O wherein the first parenthesis comprises divalent ions (indicated by the +2) of additives such as Fe, Mg, Mn, Co, Ni, Zn, Cu, or combinations of these additivesand the second parenthesis comprises trivalent ions (indicated by the +3) of additives such as Fe, Mn, Co, Ni, or combinations of these additives.

Thus, desirable magnetic spinels may take such forms as Fe O NiFe O CoFe O MnFe O (Mg, Mn) (Fe, Mn) O; etc.

These may be produced in the above-described onestep chemical reaction by additionally vaporizing suitable bromides, the reactions being exemplified by the following equations.

The apparatus of FIG. 5 may be used in deposi ing the spinels on the substrate crystal. The desired mixture by weight of dried bromides is placed in a quartz crucible 32 in roughly the ratio of the vapor pressures of the different species. The prepared substrate 20 is then placed directly over the crucible, and the assembly placed in a Vycor glass tube 34 through which the selected atmosphere flows. After a suitable purge period, the tube containing the specimen and the bromides is inserted into a splittube furnace which has been preheated.

The condi ions for deposition vary with the pariicular spinel 25 being deposited. The atmosphere flowing past the specimen is a mixture of helium, air, and Water vapor; the amount of air added to the hell-um being in the order of 0.2 to 2.0 percent, while the water vapor pressure is held constant at 24 mm. of Hg corresponding to a dew point of 25 C. The amount of air added to the flow system is controlled by accurate low-range flow gauges, and the water vapor is controlled by passing the gas mixture through water maintained at 25 C. The range of temperatures used in the deposition is from 680 C. to 720 C. The specific conditions for the deposition of the different spinels is given in FIG. 6.

Alternatively, the additives may be introduced into the first-described two-step chemical reaction as follows:

It will be noted that many of the additives have both a divalent state and a trivalent state, and therefore the same additive may appear in the first (divalent) parenthesis, or in the second (trivalent) parenthesis; e.g., (Mg,Mn) (Fe,Mn) O Their state, and therefore their position in the formula may be controlled by the amount of oxygen provided for the process. An excess of oxygen present during the process drives the additives toward their trivalent state, whereas a smaller amount of oxygen drives them toward their divalent state.

Directing attention to FIG. 7, which shows a typi:al hysteresis loop, I have found that the remanence (vertical size of the hysteresis loop) may be increased by introducing Fe and Mn into the crystalline structure; whereas Ni, Zn, and Mg additives reduce the remanence.

High coercive-field materials (those whose hysteresis loops are wide) are produced by Co additives; whereas Mn in combination with Mg reduces the coercive field.

In this way, an epitaxial ferrite having suitable magnetic properties can be formed.

Magnetic analysis of ferrite films produced in the above manner indicate that the resultant materials may have coercive fields in the range of 2 to oersteds, and remanences that range from 2000 to 4500 gauss.

Selective'heat treatment can be used to control these properties. It appears that during the formation of the thin film, the ions (30 of FIGS. 3 and 4) of the various additives do not always settle in the most desirable positions of the crystal. By heating the resultant structure, the ions are enabled to migrate to other positions of the crystal. A quenching process freezes the ions in their instantaneous position, to provide more-desirable properties.

The heat-treating process may comprise heating the structure to a given temperature, and then cooling it either quickly or at a slow rate; this result being analogous to the case-hardening and annealing heat-treatment of steels. The temperature and the cooling rates vary with each compound, and the desired results.

The resultant thin epitaxial film of magnetic material can be used for memory systems in several ways. For example, a magnetic writing head may be passed over the surface of the magnetic film to induce desired magnetic orientations at specific areas of the film. Erasing is performed by reversing the energizing magnetic field; and readout is achieved in the usual well-known manner.

An alternative memory structure 40 is shown in FIG. 8. During the processing, the magnesium oxide substrate 42 is suitably masked by use of physical masks, or by con figurations of materials such as magnesium phosphate formed on the magnesium oxide substrate, so that the deposited epitaxial magnetic film takes the form of a plurality of spaced memory elements 44. Thus, the composite element 40 comprises a non-magnetic substrate 42 of magnesium oxide, and a plurality of memory elements 44 of epitaxial magnetic material formed in the previously described manner. A grid of wires 46 and 48 criss-crosses the memory structure in such a way that wires cross in close proximity to each magnetic memory element.

When electric current is passed through selected wires, their magnetic fields are additive at their intersection, and thus induce magnetism of a particular orientation in the magnetic memory element beneath the intersection of the wires. In this way that particular memory element becomes magnetized in a particular orientation, while the other memory elements are not affected; each element acting as a single-crystal thin-film, to provide the desired magnetic characteristics previously discussed. It is also noted that wires 46 and 48 may nevertheless, at each memory element 44, be oriented to run parallel to each other as shown in FIG. 9 in order that the created magnetic fields are parallel.

Although the invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example only, and is not to be taken by way of limitation; the spirit and scope of this invention being limited only by the terms of the appended claims.

I claim:

1. The process comprising the steps of placing a crystal of MgO in a chamber;

vaporizing FeBr in said chamber;

introducing an oxygen-providing preparation into said chamber to cause the FeBr and the oxygen to combine to form FeO;

causing said FeO to deposit onto said MgO crystal positioned in said chamber; and

oxidizing said FeO to produce a crystal of Fe O that has an epitaxial relation with respect to said MgO substrate.

2. The process comprising the steps of positioning a substrate of MgO in a chamber;

vaporizing FeBr in said chamber;

introducing oxygen into said chamber to cause said FeBr and said oxygen to combine to produce FeO; causing said FeO to deposit onto said MgO substrate positioned in said chamber; and

oxidizing said FeO to produce a crystal of Fe O that has an epitaxial relation with respect to said MgO substrate. 3. The process comprising the steps of: vaporizing, in a chamber, at least one compound of the class consisting of FeBr MgBr MnBr CoBr NiBr ZnBr CuBr introducing H and sufficient oxygen into said chamber, thereby to cause a spinel ferrite to be deposited in epitaxial relation with a crystalline MgO substrate positioned in said chamber, said spinel ferrite being derived at least in part from said vaporized compound.

4. The process as defined in claim 3 wherein said deposition occurs at a reaction temperature above 500 C.

5. The process as defined in claim 3 wherein two or more of said compounds are employed in the vaporizing step.

6. The process comprising the steps of:

vaporizing, in a chamber, at least one compound of the class consisting of FeBr MgBr MnBr CoBr NiBr ZnBr CuBr introducing water vapor and sufiicient oxygen into said chamber, thereby to cause a material of the general form (A,B)+ (C,D) O wherein A and B each are divalent ions selected from the group consisting of Fe, Mg, Mn, Co, Ni, Zn and Cu and wherein C and D each are trivalent ions selected from the group consisting of'Fe, Mn, Co, and Ni, to be deposited, at a reaction temperature above 500 C., onto a crystalline MgO substrate positioned in said chamber, in an epitaxial relation with said substrate, said material being derived at least in part from said vaporized compound.

7. The process defined in claim 6 wherein an excess of oxygen is used thereby to produce a greater concentration of trivalent metal in said material.

8. The process recited in claim 6 wherein two or more of said compounds are employed in the vaporizing step.

9. The process of claim 6 including the additional step of heat treating the resultant structure in order to promote migration of the ions of said material.

10. The process of claim 6 wherein said substrate comprises a single crystal.

References Cited UNITED STATES PATENTS 2,842,468 7/1958 Brenner 148l.6 2,848,310 8/1958 Remeika 23-305 2,919,207 12/1959 Scholzel 117-406 3,047,438 7/1962 Marinace 117-106 X 3,094,395 6/1963 Richardson 23-294 3,102,099 8/1963 Stuijts 252-625 OTHER REFERENCES Cech et al.: Preparation of FeO, NiO, and C00 Crystals .by Halide Decomposition, Trans. Am. Soc. Metals, vol. 51, pp. to 161 (copy in Gr. 110, TS300 A512).

Collins et al.: Magnetic Behaviour of Thin Single- Crystal Nickel Films, Phil. Mag, vol. 45, No. 362, pp. 283-9 (copy in Science Library, Q1 P5).

WILLIAM D. MARTIN, Primary Examiner.

B. PIANALTO, Assistant Examiner. 

